CN106147672B - It is a kind of to be used to moulding/moulding compound aqueous polyurethane acrylate adhesive and preparation method thereof - Google Patents
It is a kind of to be used to moulding/moulding compound aqueous polyurethane acrylate adhesive and preparation method thereof Download PDFInfo
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- CN106147672B CN106147672B CN201510173718.5A CN201510173718A CN106147672B CN 106147672 B CN106147672 B CN 106147672B CN 201510173718 A CN201510173718 A CN 201510173718A CN 106147672 B CN106147672 B CN 106147672B
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Abstract
The invention discloses a kind of for moulding/moulding compound aqueous polyurethane acrylate adhesive and preparation method thereof, it is characterized in that, the adhesive is formed by double acrylic compounds polyurethane, acrylic monomer, styrene, emulsifier, initiator, polymerization inhibitor, pH adjusting agent, aqueous wetting agent, aqueous defoamer, deionized water through emulsion polymerization.Use homemade reactive emulsifier and double acrylic compounds polyurethane, contain double bond at molecule both ends, the aqueous binder of preparation in film forming procedure can self-crosslinking, the reticular structure of cross-linking type in formation has good water resistance, solvent resistance and cohesive strength.The adhesive has extremely strong bonding force and good water resistance between low surface tension material.It is widely used in flexible package and moulds/mould compound mechanization production process, there is high efficiency, high-quality, environmentally protective.
Description
Technical field
The present invention relates to polymer binder preparation fields, and in particular to a kind of to be used to moulding/moulding compound aqueous polyurethane
Acrylic ester adhesive and preparation method thereof.
Background technology
Chinese patent ZL201010252736.X reports a kind of polyurethane third containing ionic group of uV curable
By adding in carboxylic acid compound or sulfonate in macromolecular polyol, two are added in after dehydration for olefin(e) acid ester gum stick and preparation method thereof
Isocyanates and catalyst, add in monohydric alcohol and radical polymerization inhibitor containing acrylate group after heating, temperature control reacts
To urethane acrylate polymer, the mixture for adding in diluent and initiator obtains product.The diluent is isoborneol
Base acrylate or trimethylolpropane trimethacrylate, belong to organic solvent, will certainly bring one to environment and operating personnel
Fixed harm.
The patent ZL201010280182.4 of our company reports a kind of flexible package composite membrane ultraviolet cured water-based gluing
Agent and preparation method thereof, using epoxy-modified polyester polyurethane acrylate water-base resin as the Primary resins of adhesive, although
It is green environment protection water adhesive, but preparation method is more complicated.
The patent ZL201010280190.9 of our company reports a kind of novel reaction type emulsifier and preparation method thereof, makes
With such homemade reactive emulsifier and double acrylic compounds polyurethane, one kind has been invented by simple emulsion polymerization
For moulding/moulding compound aqueous polyurethane acrylate adhesive and preparation method thereof.The aqueous binder is without poisonous and harmful
Substance, in film forming procedure can self-crosslinking, can cure without ultraviolet light, and with good water resistance, resistance to
Solvent borne and cohesive strength.
Invention content
The problem of being encountered for current aqueous binder industry prior art, it is multiple for moulding/moulding the present invention provides one kind
Aqueous polyurethane acrylate adhesive of conjunction and preparation method thereof.
It is described that technical scheme is as follows：It is a kind of to be used to moulding/moulding compound aqueous polyurethane acrylate adhesive,
It is characterized in that, the adhesive is by double acrylic compounds polyurethane, acrylic monomer, styrene, emulsifier, initiator, inhibition
Agent, pH adjusting agent, aqueous wetting agent, aqueous defoamer, deionized water are formed through emulsion polymerization.The adhesive is to low surface
There is extremely strong bonding force and good water resistance between dead-wood material.
The dosage of each raw material is by weight percentage in the aqueous polyurethane acrylate adhesive：
The structural formula of double acrylic compounds polyurethane is as follows：
N=1~5 in formula, A be polyester group or polyether group, R1And R2Linear chain or branch chain for carbon atom number 1~18
Alkane, R3For hydrogen atom or methyl, R4For any one in following structural formula：
The acrylic monomer is acrylic acid, butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, acrylic acid
Any one or more in hydroxyl ethyl ester, hydroxypropyl acrylate, methacrylic acid；
The emulsifier is homemade reactive emulsifier；
The initiator is one kind in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate；
The polymerization inhibitor is 4- metoxyphenols；
The pH adjusting agent is ammonium hydroxide；
The aqueous wetting agent is polyether-modified dimethyl silicone polymer type wetting agent；
The aqueous defoamer is butynediols class antifoaming agent.
Described is a kind of for moulding/moulding the preparation method of compound aqueous polyurethane acrylate adhesive, and feature exists
In including the following steps：
Each raw material is weighed by proportioning, in emulsifying kettle, adds in the deionization for accounting for whole deionized water total weights 10~20%
Water opens stirring, adds in and accounts for the emulsifiers of whole emulsifier total weights 80~90%, then add in double acrylic compounds polyurethane,
Acrylic monomer, styrene, stir evenly to form emulsion；
The deionized water for accounting for ionized water total weight 70~80% is added in a kettle, is opened stirring, is warming up to 80 DEG C,
Add in remaining emulsifier and whole polymerization inhibitors；It is water-soluble that the deionized water dissolving of 20 times of weight of initiator is first formed initiator
Liquid is added to the 70~80% of whole initiator solutions in reaction kettle, takes the 10~15% of whole emulsions to be added drop-wise to instead
It answers in kettle, time for adding 30 minutes, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；
In insulating process, remaining initiator solution is added in emulsifying kettle, stirs evenly to be formed containing initiator
Emulsion, the emulsion droplet containing initiator is added in reaction kettle, dripped off at 3.5~4 hours it is complete, reaction temperature control exists
79~81 DEG C；Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, being adjusted with pH adjusting agent
PH value 6.0~7.0 adds in aqueous wetting agent and aqueous defoamer, stirs evenly and bonded to get to aqueous polyurethane acrylate
Agent.
The beneficial effects of the present invention are：Using homemade reactive emulsifier and double acrylic compounds polyurethane, in molecule
Double bond is contained at both ends, the aqueous binder of preparation in film forming procedure can self-crosslinking, the reticular structure of cross-linking type in formation,
With good water resistance, solvent resistance and cohesive strength.The adhesive is to polyethylene, polypropylene, polyester, nylon, aluminium foil etc.
There is extremely strong bonding force and good water resistance between low surface tension material.It is widely used in flexible package and moulds/mould compound machine
Tool production process has the advantages that high efficiency, high-quality, environmentally protective.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail：
Embodiment 1
In emulsifying kettle, deionized water 3000g is added in, stirring is opened, adds in homemade reactive emulsifier 250g, then
Add in double acrylic compounds polyurethane 1200g, acrylic acid 500g, ethyl acrylate 12000g, butyl acrylate 2500g, acrylic acid
Hydroxyl ethyl ester 2000g, styrene 5000g, stir evenly to form emulsion；
Deionized water 15600g is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 50g and polymerization inhibitor 4- metoxyphenols 5g；It is water-soluble that 120g ammonium persulfates 2400g deionized water dissolvings are first formed initiator
Liquid, then 2000g initiator solutions are added in reaction kettle；3000g emulsion droplets is taken to be added in reaction kettle, time for adding 30
Minute, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；In insulating process, remaining 520g initiators
Aqueous solution is added in emulsifying kettle, stirs evenly to form the emulsion containing initiator, and the emulsion containing initiator is added dropwise
It into reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature is controlled at 79~81 DEG C；Subsequent continuous insulation reaction is added dropwise
30~60 minutes, 40 DEG C were then cooled to hereinafter, adjusting pH value 6.72, addition 80g aqueous wetting agents and 50g water with 350g ammonium hydroxide
Property antifoaming agent is stirred evenly to get to aqueous polyurethane acrylate adhesive.
Embodiment 2
In emulsifying kettle, deionized water 4500g is added in, stirring is opened, adds in homemade reactive emulsifier 400g, then
Add in double acrylic compounds polyurethane 1800g, methacrylic acid 1000g, butyl acrylate 10000g, Isooctyl acrylate monomer 2000g,
Hydroxypropyl acrylate 3000g, styrene 7500g, stir evenly to form emulsion；
Deionized water 16500g is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 50g and polymerization inhibitor 4- metoxyphenols 5g；It is water-soluble that 100g sodium peroxydisulfates 2000g deionized water dissolvings are first formed initiator
Liquid, then 1500g initiator solutions is taken to be added in reaction kettle；4000g emulsion droplets is taken to be added in reaction kettle, time for adding 30
Minute, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；
In insulating process, remaining 600g initiator solutions are added in emulsifying kettle, stir evenly to be formed containing drawing
The emulsion of agent is sent out, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature
Control is at 79~81 DEG C；
Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with 250g ammonium hydroxide
Value 6.57 adds in 120g aqueous wetting agents and 50g aqueous defoamers, stirs evenly and glued to get to aqueous polyurethane acrylate
Mixture.
Embodiment 3
In emulsifying kettle, deionized water 2000g is added in, stirring is opened, adds in homemade reactive emulsifier 65g, then
Double acrylic compounds polyurethane 1300g, butyl acrylate 9000g, styrene 12500g are added in, stirs evenly to form emulsion；
Deionized water 14000g is added in reaction kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade reactive emulsifier 15g and resistance
Poly- agent 4- metoxyphenols 5g；200g potassium peroxydisulfates 4000g deionized water dissolvings are first formed initiator solution, then take
3000g initiator solutions are added in reaction kettle；3000g emulsion droplets is taken to be added in reaction kettle, time for adding 30 minutes, instead
Temperature control is answered to continue insulation reaction 30 minutes at 79~81 DEG C；
In insulating process, remaining 1200g initiator solutions are added in emulsifying kettle, stir evenly to be formed containing drawing
The emulsion of agent is sent out, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature
Control is at 79~81 DEG C；
Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with 300g ammonium hydroxide
Value 6.83 adds in 200g aqueous wetting agents and 80g aqueous defoamers, stirs evenly and glued to get to aqueous polyurethane acrylate
Mixture.
Embodiment 4
In emulsifying kettle, deionized water 3500g is added in, stirring is opened, adds in homemade reactive emulsifier 180g, then
Add in double acrylic compounds polyurethane 500g, methacrylic acid 1000g, ethyl acrylate 8000g, butyl acrylate 2000, propylene
Sour hydroxyl ethyl ester 1000g, styrene 8000g, stir evenly to form emulsion；
Deionized water 14500g is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 20g and polymerization inhibitor 4- metoxyphenols 5g；It is water-soluble that 100g ammonium persulfates 2000g deionized water dissolvings are first formed initiator
Liquid, then 1500g initiator solutions is taken to be added in reaction kettle；3000g emulsion droplets is taken to be added in reaction kettle, time for adding 30
Minute, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；
In insulating process, remaining 600g initiator solutions are added in emulsifying kettle, stir evenly to be formed containing drawing
The emulsion of agent is sent out, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature
Control is at 79~81 DEG C；Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, with 400g ammonium hydroxide
PH value 6.97 is adjusted, adds in 250g aqueous wetting agents and 50g aqueous defoamers, is stirred evenly to get to aqueous polyurethane propylene
Acid esters adhesive.
Embodiment 5
In emulsifying kettle, deionized water 3000g is added in, stirring is opened, adds in homemade reactive emulsifier 170g, then
Add in double acrylic compounds polyurethane 1000g, acrylic acid 1000g, methacrylic acid 10000g, ethyl acrylate 500g, acrylic acid
Butyl ester 1500g, Isooctyl acrylate monomer 3000g, hydroxy-ethyl acrylate 1000g, hydroxypropyl acrylate 2000g, styrene 5000g,
It stirs evenly to form emulsion；
Deionized water 18000g is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 30g and polymerization inhibitor 4- metoxyphenols 5g；It is water-soluble that 100g sodium peroxydisulfates 2000g deionized water dissolvings are first formed initiator
Liquid, then 1500g initiator solutions is taken to be added in reaction kettle；3000g emulsion droplets is taken to be added in reaction kettle, time for adding 30
Minute, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；
In insulating process, remaining 600g initiator solutions are added in emulsifying kettle, stir evenly to be formed containing drawing
The emulsion of agent is sent out, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature
Control is at 79~81 DEG C；
Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with 800g ammonium hydroxide
Value 6.96 adds in 300g aqueous wetting agents and 60g aqueous defoamers, stirs evenly and glued to get to aqueous polyurethane acrylate
Mixture.
Embodiment 6
In emulsifying kettle, deionized water 2800g is added in, stirring is opened, adds in homemade reactive emulsifier 160g, then
Add in double acrylic compounds polyurethane 800g, butyl acrylate 10000g, hydroxypropyl acrylate 500g, hydroxy-ethyl acrylate 1000g,
Methacrylic acid 500g, styrene 10000g, stir evenly to form emulsion；
Deionized water 18200g is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 40g and polymerization inhibitor 4- metoxyphenols 5g；It is water-soluble that 200g ammonium persulfates 4000g deionized water dissolvings are first formed initiator
Liquid, then 3000g initiator solutions is taken to be added in reaction kettle；3000g emulsion droplets is taken to be added in reaction kettle, time for adding 30
Minute, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；
In insulating process, remaining 1200g initiator solutions are added in emulsifying kettle, stir evenly to be formed containing drawing
The emulsion of agent is sent out, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature
Control is at 79~81 DEG C；
Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with 250g ammonium hydroxide
Value 6.29 adds in 100g aqueous wetting agents and 60g aqueous defoamers, stirs evenly and glued to get to aqueous polyurethane acrylate
Mixture.
Embodiment 7
In emulsifying kettle, deionized water 500kg is added in, stirring is opened, adds in homemade reactive emulsifier 70kg, then
Add in double acrylic compounds polyurethane 100kg, methacrylic acid 200kg, ethyl acrylate 200kg, butyl acrylate 1800kg, third
The different monooctyl ester 300kg of olefin(e) acid, hydroxy-ethyl acrylate 300kg, hydroxypropyl acrylate 200kg, styrene 2000kg, stir evenly to be formed
Emulsion；
Deionized water 3600kg is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 10kg and polymerization inhibitor 4- metoxyphenols 1kg；20kg sodium peroxydisulfates 400kg deionized water dissolvings are first formed initiator water
Solution, then 300kg initiator solutions is taken to be added in reaction kettle；700kg emulsion droplets is taken to be added in reaction kettle, time for adding
30 minutes, reaction temperature was controlled at 79~81 DEG C, continued insulation reaction 30 minutes；In insulating process, remaining 120kg is caused
Agent aqueous solution is added in emulsifying kettle, stirs evenly to form the emulsion containing initiator, the emulsion droplet containing initiator
It is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature is controlled at 79~81 DEG C；
Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with 80kg ammonium hydroxide
Value 6.56 adds in 20kg aqueous wetting agents and 10kg aqueous defoamers, stirs evenly and glued to get to aqueous polyurethane acrylate
Mixture.
Embodiment 8
In emulsifying kettle, deionized water 800kg is added in, stirring is opened, adds in homemade reactive emulsifier 40kg, then
Add in double acrylic compounds polyurethane 200kg, butyl acrylate 1000kg, hydroxypropyl acrylate 500kg, hydroxy-ethyl acrylate
1000kg, styrene 1000kg, stir evenly to form emulsion；
Deionized water 4100kg is added in a kettle, stirring is opened, is warming up to 80 DEG C, adds in homemade response type emulsification
Agent 10kg and polymerization inhibitor 4- metoxyphenols 1kg；30kg ammonium persulfates 600kg deionized water dissolvings are first formed initiator water
Solution, then 480kg initiator solutions is taken to be added in reaction kettle；500kg emulsion droplets is taken to be added in reaction kettle, time for adding
30 minutes, reaction temperature was controlled at 79~81 DEG C, continued insulation reaction 30 minutes；
In insulating process, remaining 150kg initiator solutions are added in emulsifying kettle, stir evenly to be formed containing drawing
The emulsion of agent is sent out, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature
Control is at 79~81 DEG C；
Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with 100kg ammonium hydroxide
Value 6.81 adds in 30kg aqueous wetting agents and 10kg aqueous defoamers, stirs evenly and glued to get to aqueous polyurethane acrylate
Mixture.
Homemade reactive emulsifier in above-described embodiment 1~8 is the patented product of our company, refers to patent
ZL201010280190.9, aqueous wetting agent are polyether-modified dimethyl silicone polymer type wetting agent, and aqueous defoamer is butine
Glycols antifoaming agent.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the invention as claimed with
Modification should all belong to the covering scope of the claims in the present invention.
Claims (2)
1. a kind of be used to moulding/moulding compound aqueous polyurethane acrylate adhesive, which is characterized in that the adhesive is by double propylene
Acids polyurethane, acrylic monomer, styrene, emulsifier, initiator, polymerization inhibitor, pH adjusting agent, aqueous wetting agent, water
Property antifoaming agent, deionized water formed through emulsion polymerization, which has polyethylene, polypropylene, polyester, nylon extremely strong viscous
Relay and good water resistance；
The dosage of each raw material is by weight percentage in the aqueous polyurethane acrylate adhesive：
The structural formula of double acrylic compounds polyurethane is as follows：
N=1~5 in formula, A be polyester group or polyether group, R1And R2For the linear chain or branch chain alkane of carbon atom number 1~18,
R3For hydrogen atom or methyl, R4For any one in following structural formula：
The acrylic monomer is acrylic acid, butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, acrylic acid hydroxyl second
Any one or more in ester, hydroxypropyl acrylate, methacrylic acid；
The emulsifier is homemade reactive emulsifier；
The initiator is one kind in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate；
The polymerization inhibitor is 4- metoxyphenols；
The pH adjusting agent is ammonium hydroxide；
The aqueous wetting agent is polyether-modified dimethyl silicone polymer type wetting agent；
The aqueous defoamer is butynediols class antifoaming agent.
2. it is as described in claim 1 a kind of for moulding/moulding the preparation method of compound aqueous polyurethane acrylate adhesive,
It is characterized by comprising the following steps：
Each raw material is weighed by proportioning, in emulsifying kettle, the deionized water for accounting for whole deionized water total weights 10~20% is added in, opens
Stirring is opened, adds in the emulsifier for accounting for whole emulsifier total weights 80~90%, then adds in double acrylic compounds polyurethane, acrylic acid
Class monomer, styrene, stir evenly to form emulsion；
The deionized water for accounting for ionized water total weight 70~80% is added in a kettle, opens stirring, is warming up to 80 DEG C, is added in
Remaining emulsifier and whole polymerization inhibitors；The deionized water dissolving of 20 times of weight of initiator is first formed initiator solution,
It is added in reaction kettle the 70~80% of whole initiator solutions, takes the 10~15% of whole emulsions to be added drop-wise to reaction kettle
In, time for adding 30 minutes, reaction temperature is controlled at 79~81 DEG C, continues insulation reaction 30 minutes；
In insulating process, remaining initiator solution is added in emulsifying kettle, stirs evenly to form the breast containing initiator
Change liquid, the emulsion droplet containing initiator is added in reaction kettle, was added dropwise at 3.5~4 hours, reaction temperature is controlled 79
~81 DEG C；Subsequent continuous insulation reaction is added dropwise 30~60 minutes, is then cooled to 40 DEG C hereinafter, adjusting pH with pH adjusting agent
Value 6.0~7.0 adds in aqueous wetting agent and aqueous defoamer, stirs evenly and bonded to get to aqueous polyurethane acrylate
Agent.
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| CN106810647B (en) * | 2016-12-27 | 2020-08-11 | 东莞市浩彩油墨科技有限公司 | Water-based ink resin binder and preparation method thereof |
| CN106674437A (en) * | 2016-12-31 | 2017-05-17 | 佛山市顺德区巴德富实业有限公司 | Polyurethane-acrylate hybrid emulsion and preparation method thereof |
| CN109705278B (en) * | 2018-12-26 | 2021-10-08 | 广东衡光新材料科技有限公司 | Water-based acrylic emulsion for automobile electrophoresis finish paint and preparation method thereof |
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| CN101864025A (en) * | 2010-06-21 | 2010-10-20 | 东莞市凯迪克高分子材料有限公司 | Preparation method of polyacrylate microgel emulsion and application thereof |
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| CN103059784A (en) * | 2013-02-01 | 2013-04-24 | 东莞市星宇高分子材料有限公司 | Water-based plastic-plastic compound adhesive for food and drug flexible package and preparation method thereof |
| CN103275653A (en) * | 2013-05-13 | 2013-09-04 | 浙江科冠聚合物有限公司 | Acrylic plastic-plastic composite latex |
| CN103865448A (en) * | 2014-03-27 | 2014-06-18 | 山东华诚高科胶粘剂有限公司 | Aqueous composite adhesive and preparation method for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101704923A (en) * | 2009-11-18 | 2010-05-12 | 北京高盟化工有限公司 | Water-based acrylic acid emulsion, water-based adhesive for aluminum-plating film composite material and preparation method thereof |
| CN101864025A (en) * | 2010-06-21 | 2010-10-20 | 东莞市凯迪克高分子材料有限公司 | Preparation method of polyacrylate microgel emulsion and application thereof |
| CN102618193A (en) * | 2012-04-16 | 2012-08-01 | 广州荣域实业有限公司 | Water-based composite adhesive |
| CN103059784A (en) * | 2013-02-01 | 2013-04-24 | 东莞市星宇高分子材料有限公司 | Water-based plastic-plastic compound adhesive for food and drug flexible package and preparation method thereof |
| CN103275653A (en) * | 2013-05-13 | 2013-09-04 | 浙江科冠聚合物有限公司 | Acrylic plastic-plastic composite latex |
| CN103865448A (en) * | 2014-03-27 | 2014-06-18 | 山东华诚高科胶粘剂有限公司 | Aqueous composite adhesive and preparation method for same |
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